JP5682095B2 - Coating layer and coating layer forming method - Google Patents

Description

The present invention relates to a coating layer and a coating layer forming method, and more particularly to a coating layer applied to a base material such as a vehicle exterior and a method for forming the coating layer.

Conventionally, coating treatments using various treatment agents have been performed in order to impart water repellency, gloss, and luster to exteriors of vehicles used outdoors such as automobiles and industrial vehicles, for example, painted surfaces of automobiles. . For example, after applying an amino-modified silicone oil emulsion, after applying and drying a coating agent mainly composed of amino-modified silicone oil, a coating method of a water-repellent agent for vehicle exterior in which other emulsions are applied repeatedly (Patent Document 1) A method for polishing a painted surface of a vehicle (Patent Document 2), comprising a water-based emulsion containing dimethyl silicone oil and an amino-modified silicone oil, applying and drying a polishing agent on the painted surface of the vehicle, and amino-modified silicone oil A method of forming a water-slidable coating film made of silicone on a substrate surface by applying an anionic silica fine particle dispersion after coating the emulsion on the base surface is known (Patent Document 3). In these methods, an agent mainly composed of amino-modified silicone oil is first applied to a substrate, for example, a vehicle painted surface. In these methods, two different types of agents are overcoated, but the preservability of each agent is insufficient, and there is a problem in workability when applying each agent.

Various coating agent compositions that give water repellency and gloss to the painted surface of vehicles are also known. For example, Patent Document 4 describes a polishing water repellent composition containing dimethylpolysiloxane, amino-modified dimethylpolysiloxane, and acids, alcohols and water in amounts necessary for neutralization of amino-modified dimethylpolysiloxane. ing. Patent Document 5 describes a vehicle coating agent containing a predetermined amount of a moisture curable silicone oligomer, a curing catalyst, and a both-end type reactive silicone oil. Here, the reactive functional group contained in the both-end type reactive silicone oil includes a hydroxyl group, a carbinol group (—R ⁵ OH, R ⁵ represents an alkylene group), an aminoalkyl group (—R ⁶ NH ₂ , R ⁶ represents an alkylene group) and a carboxyalkyl group (—R ⁷ COOH, R ⁷ represents an alkylene group). Patent Document 6 discloses polydimethylsiloxane having a trifunctional hydrolyzable group at both ends, a partial hydrolysis condensate of alkoxysilane having 1 to 4 hydrolyzable groups, an organic titanium catalyst, aliphatic carbonization. A water-repellent coating silicone composition comprising a hydrogen solvent, an ester solvent, or an alcohol solvent is described. Patent Document 7 discloses an emulsion type in which a predetermined amount of amino-modified silicone oil and dimethyl silicone oil having a predetermined viscosity at 25 ° C. is dispersed in water, and the average particle diameter of oil droplets is a predetermined value. A polish is described. Patent Document 8 describes a water repellent composition comprising a both-end-type reactive polyorganosiloxane, a metal alkoxide curing catalyst, and an alcohol solvent. Patent Document 9 describes a surface water-repellent protective agent containing a predetermined amount of a moisture-curable liquid silicone oligomer, a curing catalyst, a linear modified polydimethylsiloxane containing both terminal silanol groups, and a predetermined volatile solvent. Yes. Patent Document 10 describes a water repellent treatment agent comprising a silicone emulsion emulsified with a silicone containing amino-modified silicone, a water-soluble organic solvent such as alcohol, and a surfactant. The water-repellent treatment agent does not require a conventional ground treatment or the like, and directly applies the agent to a substrate to exhibit good water repellency alone. These agents are so-called one-part water-repellent treatment agents. However, when a surfactant or acid is used in the agent, the adhesion to the coating film is deteriorated, and the water repellency and gloss are sufficient. There were problems such as not.

JP 2005-28337 A JP 2005-29695 A JP 2006-247544 A Japanese Patent Laid-Open No. 11-80668 JP 2008-75021 A JP 2002-356651 A JP-A 64-75576 Japanese Patent Laid-Open No. 7-305053 JP 2009-138063 A JP 2001-11435 A

The present invention provides a coating layer capable of imparting excellent water repellency and good gloss to a substrate such as a vehicle exterior, and is excellent in storage stability and dispersibility of the agent used, and Provided is a method for forming a coating layer, which not only has excellent workability at the time of application, but also allows the obtained coating layer to impart excellent water repellency and good gloss to a substrate such as a vehicle exterior. Is.

In order to solve the above-mentioned problems, the present inventor examined what problems exist in various conventional coating agents and coating methods. As a result, as described above, two different types of agents are overcoated, and an agent mainly composed of amino-modified silicone oil is first applied to a substrate, for example, a vehicle painted surface. In this case, the storage stability of each agent was insufficient, and it was found that there was a problem in workability when applying each agent. On the other hand, it has also been found that the one-component water repellent treatment agent as described above has a problem that water repellency and gloss cannot be sufficiently increased. The inventor conducted further studies to solve these problems, and as a result, a one-part water-repellent treatment agent, that is, a surface that does not undergo overcoating, no matter how carefully and carefully it is treated, etc. It has been found that the improvement in water repellency and gloss is limited because the inhomogeneous portion occurring in the film cannot be removed. On the other hand, in adopting a method of repeatedly coating two different types of agents, it is important that each agent is excellent in storage stability and dispersibility, and each agent has no odor and is wiped off. It is not only necessary to be excellent in workability so as to be easy to raise, but the second layer sufficiently complements the heterogeneous portion generated in the first layer, and the second layer is the first layer. It has been found that it is necessary to improve the water repellency and gloss without impeding the water. The present inventor further studied from the viewpoints described above and, in particular, from what viewpoint can be obtained a coating layer having suitable water repellency and gloss when combined, and the following predetermined ones were obtained. When the two layers are combined to form two layers, the two layers interact, and the resulting coating layer has excellent water repellency and good gloss. When the coating layer forming method is used, the agent to be applied is excellent in storage stability and dispersibility, has no odor, and has excellent workability at the time of application, and the present invention has been completed. .

That is, the present invention
(1) (a-1) 3-45 parts by mass of a polyorganosiloxane having one or more hydrolyzable functional groups in the molecule,
(A-2) Curing catalyst 0.05 to 5 parts by mass, and (a-3) consisting of a saturated hydrocarbon solvent having 8 to 15 carbon atoms and an aromatic hydrocarbon solvent having 8 to 15 carbon atoms, Film forming agent (A) comprising a total of 100 parts by mass of 50 to 96.95 parts by mass of an organic solvent in which the mass ratio of the saturated hydrocarbon solvent to the aromatic hydrocarbon solvent is 100/0 to 50/50
Layer (I) obtained by curing
And
(B-1) Polyorganosiloxane having one or more amino groups in the molecular side chain (however, when (b-2) has an amino group in the molecular side chain, it does not have two or more amino groups at the end of the molecular chain. .) 0.05 to 15 parts by mass,
(B-2) 0.01 to 10 parts by mass of a polyorganosiloxane having two or more amino groups at the molecular chain terminal,
(B-3) Silicone resin emulsion emulsified with a nonionic or anionic surfactant 1 to 20 parts by mass as a solid content,
(B-4) Finishing agent (B) containing a total of 100 parts by mass of a hydrophilic group-containing organic solvent 0.1 to 25 parts by mass and (b-5) 30 to 98.84 parts by mass of water
Layer obtained by solidifying (II)
And a layer (I) on the substrate side and a layer (II) on the surface side.

As a preferred embodiment,
(2) The coating layer according to the above (1), comprising the layer (I) on the substrate and the layer (II) thereon.
(3) The above (1) or (2), wherein the layer (I) has a thickness of 0.1 to 0.5 μm, and the layer (II) has a thickness of 0.1 to 0.5 μm. Coating layer,
(4) Coating as described in any one of said (1)-(3) whose compounding quantity of component (a-1) is 5-45 mass parts in 100 mass parts of film formation agents (A). layer,
(5) Coating as described in any one of said (1)-(3) whose compounding quantity of component (a-1) is 7-45 mass parts in 100 mass parts of film forming agents (A). layer,
(6) Coating as described in any one of said (1)-(3) whose compounding quantity of component (a-1) is 7-30 mass parts in 100 mass parts of film formation agents (A). layer,
(7) The amount of component (b-1) is 0.1 to 5 parts by mass in 100 parts by mass of the finishing agent (B), as described in any one of (1) to (6) above. Coating layer,
(8) The blending amount of the component (b-2) is 0.1 to 3 parts by mass in 100 parts by mass of the finishing agent (B), as described in any one of (1) to (7) above. Coating layer,
(9) Said (1)-(8) whose sum total of compounding quantity of component (b-1) and (b-2) is 0.06-20 mass parts in 100 mass parts of finishing agents (B). ) Coating layer according to any one of
(10) Coating as described in any one of said (1)-(9) whose compounding quantity of component (b-3) is 3-15 mass parts in 100 mass parts of finishing agents (B). layer,
(11) The coating layer according to any one of the above (1) to (10), wherein the saturated hydrocarbon solvent having 8 to 15 carbon atoms constituting the component (a-3) is an isoparaffin solvent,
(12) The coating layer according to any one of (1) to (11) above, wherein the component (a-3) comprises 100 parts by mass of a saturated hydrocarbon solvent having 8 to 15 carbon atoms,
(13) The coating layer according to any one of the above (1) to (12), wherein the component (b-4) is alcohol,
(14) The coating layer according to any one of (1) to (13), wherein the component (a-1) is polydimethylsiloxane having hydrolyzable functional groups at both ends of the molecular chain.
(15) The coating layer according to any one of (1) to (13), wherein the component (a-1) is a polydimethylsiloxane containing methoxy groups at both ends of the molecular chain,
(16) The coating layer according to any one of (1) to (15), wherein the component (a-2) is an organometallic compound,
(17) The coating layer according to any one of (1) to (16), wherein the base material is a vehicle exterior.

The present invention also provides
(18) (a-1) 3-45 parts by mass of a polyorganosiloxane having one or more hydrolyzable functional groups in the molecule,
(A-2) Curing catalyst 0.05 to 5 parts by mass, and (a-3) consisting of a saturated hydrocarbon solvent having 8 to 15 carbon atoms and an aromatic hydrocarbon solvent having 8 to 15 carbon atoms, Film forming agent (A) comprising a total of 100 parts by mass of 50 to 96.95 parts by mass of an organic solvent in which the mass ratio of the saturated hydrocarbon solvent to the aromatic hydrocarbon solvent is 100/0 to 50/50
(I), which is applied onto a substrate and then dried at ambient temperature for 5 to 90 minutes to form layer (I),
And
(B-1) Polyorganosiloxane having one or more amino groups in the molecular side chain (however, when (b-2) has an amino group in the molecular side chain, it does not have two or more amino groups at the end of the molecular chain. .) 0.05 to 15 parts by mass,
(B-2) 0.01 to 10 parts by mass of a polyorganosiloxane having two or more amino groups at the molecular chain terminal,
(B-3) Silicone resin emulsion emulsified with a nonionic or anionic surfactant 1 to 20 parts by mass as a solid content,
(B-4) Finishing agent (B) containing a total of 100 parts by mass of a hydrophilic group-containing organic solvent 0.1 to 25 parts by mass and (b-5) 30 to 98.84 parts by mass of water
Step (II) in which layer (II) is applied on the layer (I) and then dried at ambient temperature for 10 minutes or more.
Is a method for forming a coating layer.

As a preferred embodiment,
(19) The coating agent (A) is applied in the step (I) using a dry cloth, and the finishing agent (B) is applied in the step (II) using a compress. The coating layer forming method according to (18) above,
(20) The coating layer forming method according to the above (18) or (19), wherein the amount of the film forming agent (A) used in the step (I) is 0.1 to 10 ml per 1 m ^{2 of} the base material.
(21) The coating according to any one of (18) to (20) above, wherein the amount of the finishing agent (B) used in the step (II) is 0.1 to 10 ml per 1 m ^{2 of} the base material. Layer forming method,
(22) The coating according to any one of the above (18) to (21), wherein the blending amount of the component (a-1) is 5 to 45 parts by mass in 100 parts by mass of the film forming agent (A). Layer forming method,
(23) The coating according to any one of (18) to (21) above, wherein the compounding amount of component (a-1) is 7 to 45 parts by mass in 100 parts by mass of the film forming agent (A). Layer forming method,
(24) The coating according to any one of (18) to (21) above, wherein the amount of component (a-1) is 7 to 30 parts by mass in 100 parts by mass of the film forming agent (A). Layer forming method,
(25) The blending amount of component (b-1) is 0.1 to 5 parts by mass in 100 parts by mass of the finishing agent (B), as described in any one of (18) to (24) above. Coating layer forming method,
(26) The amount of component (b-2) is 0.1 to 3 parts by mass in 100 parts by mass of the finishing agent (B), as described in any one of (18) to (25) above. Coating layer forming method,
(27) Said (18)-(26) whose sum total of compounding quantity of component (b-1) and (b-2) is 0.06-20 mass parts in 100 mass parts of finishing agents (B). ) The coating layer forming method according to any one of
(28) The coating amount according to any one of (18) to (27) above, wherein the amount of component (b-3) is 3 to 15 parts by mass in 100 parts by mass of the finishing agent (B). Layer forming method,
(29) The coating layer forming method according to any one of (18) to (28), wherein the saturated hydrocarbon solvent having 8 to 15 carbon atoms constituting component (a-3) is an isoparaffin solvent. ,
(30) The coating layer according to any one of the above (18) to (29), wherein the component (a-3) comprises 100 parts by mass of a saturated hydrocarbon solvent having 8 to 15 carbon atoms,
(31) The coating layer forming method according to any one of (18) to (30), wherein the component (b-4) is alcohol,
(32) The coating layer according to any one of (18) to (31), wherein component (a-1) is polydimethylsiloxane having hydrolyzable functional groups at both ends of the molecular chain.
(33) The coating layer forming method according to any one of (18) to (31), wherein the component (a-1) is a polydimethylsiloxane containing methoxy groups at both ends of the molecular chain,
(34) The coating layer forming method according to any one of (18) to (33), wherein the component (a-2) is an organometallic compound,
(35) The coating layer forming method according to any one of (18) to (34), wherein the base material is a vehicle exterior.
Can be mentioned.

The coating layer of the present invention can impart excellent water repellency and good gloss to a substrate such as a vehicle exterior. The coating layer forming method of the present invention is not only excellent in storage stability and dispersibility of the agent used and excellent in workability at the time of application, but the obtained coating layer is a substrate, for example, a vehicle exterior. For example, it can impart excellent water repellency and good gloss.

The coating layer of the present invention comprises at least a layer (I) obtained by curing the film forming agent (A) and a layer (II) obtained by solidifying the finishing agent (B), and a substrate. The layer (I) is provided on the side, and the layer (II) is provided on the surface side, that is, the side closer to the atmosphere as compared with the layer (I). Here, the film forming agent (A) is (a-1) a polyorganosiloxane having one or more hydrolyzable functional groups in the molecule, (a-2) a curing catalyst, and (a-3) carbon number. It consists of 8-15 saturated hydrocarbon solvents and C8-15 aromatic hydrocarbon solvents, and the mass ratio of the saturated hydrocarbon solvent to the aromatic hydrocarbon solvent is 100 / 0-50 / A total of 100 parts by mass of 50 organic solvents is included. On the other hand, the finishing agent (B) is (b-1) a polyorganosiloxane having one or more amino groups in the molecular side chain (however, when (b-2) has an amino group in the molecular side chain, the molecular chain Emulsified by polyorganosiloxane having two or more amino groups at the molecular chain end, (b-3) nonionic or anionic surfactant. A silicone resin emulsion, (b-4) hydrophilic group containing organic solvent, and (b-5) 100 parts by mass of water in total are included.

The (a-1) polyorganosiloxane contained in the film forming agent (A) may be any one having at least one hydrolyzable functional group in the molecule. The number of hydrolyzable functional groups is preferably 2-6. The hydrolyzable functional group may be present at either the main chain end or the side chain of the polyorganosiloxane molecule. Since it is excellent in strength after film formation, it is preferably present at the end of the molecular chain. Examples of the hydrolyzable functional group include an alkoxy group, an aminoxy group, a ketoxime group, an alkenyloxy group, an amide group, and an acetoxy group. A preferable hydrolyzable functional group is an alkoxy group, more preferably a methoxy group, an ethoxy group, or a propoxy group. By using a polyorganosiloxane having such a group, it is possible to achieve even better curing and to reduce odor during operation. The component (a-1) is preferably a polyorganosiloxane having a hydrolyzable functional group at both ends of the molecular chain, more preferably a methoxy group. The viscosity (25 ° C.) of the component (a-1) is a value measured according to JIS Z 8803, and the upper limit is preferably 1,000 mm ² s ⁻¹ , more preferably 500 mm ² s ^−1. Is preferably 10 mm ² s ⁻¹ , more preferably 50 mm ² s ⁻¹ .

(A-2) The curing catalyst is preferably an organometallic compound. As the organometallic compound, for example, various compounds such as tin, titanium, aluminum, zirconium, lead and the like can be used. Examples of the tin compound include tin octylate, dibutyltin diacetate, dibutyltin dioctylate, dibutyltin dilaurate, dibutyltin malate, and dibutyltin bisoctyloxycarbonylmethylthiolate. Examples of titanium compounds include tetrabutyl titanate, tetramethoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium, tetrakis (ethylene glycol monomethyl ether) titanate, tetrakis (ethylene glycol monoethyl ether) titanate. Tetrakis (ethylene glycol monobutyl ether) titanate, diisopropoxybis (acetylacetonate) titanate, diisopropoxybis (ethylacetoacetate) titanate, tetrakis (2-butoxyethyl alcoholate) titanate, and the like. Examples of the aluminum compound include trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, diisopropoxy (ethylacetoacetate) aluminum, isopropoxybis (ethylacetoacetate) aluminum, tris (ethylacetoacetate) aluminum, tris ( Acetylacetone) aluminum and the like. Examples of zirconium compounds include acetylacetone zirconium, triscetylacetone zirconium, tetrakis (ethylene glycol monomethyl ether) zirconium, tetrakis (ethylene glycol monoethyl ether) zirconium, tetrakis (ethylene glycol monobutyl ether) zirconium, dibutoxybis (ethyl acetoacetate) zirconium. , Tetrakis (2-butoxyethyl alcoholate) zirconium and the like. Examples of the lead compound include lead octylate and lead naphthenate. These compounds are not particularly limited as long as they can impart desired properties to the finally formed coating layer. In the present invention, a titanium compound is preferably used.

In addition to the organometallic compound, (a-2) the curing catalyst further includes (a-1) a compound that causes a curing reaction to polyorganosiloxane having one or more hydrolyzable functional groups in the molecule. You can also. The upper limit of the compounding amount of the compound is preferably 10 parts by weight, more preferably 5 parts by weight, and the lower limit is preferably 0.001 parts by weight, more preferably 0.01 parts by weight with respect to 100 parts by weight of the organometallic compound. Part by mass. Examples of the compound include butylamine, dibutylamine, hexylamine, t-butylamine, ethylenediamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, ethylenediamine, triethylenediamine, imidazole, isophoronediamine, ammonia, sodium hydroxide, hydroxide. Examples include potassium, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, monoalkyl phosphorous acid, dialkyl phosphorous acid, p-toluenesulfonic acid, trichloroacetic acid, and fluorine compounds. In the present invention, these can be appropriately selected and used.

(A-3) The organic solvent is composed of a saturated hydrocarbon solvent having 8 to 15 carbon atoms and an aromatic hydrocarbon solvent having 8 to 15 carbon atoms as an optional component. The mass ratio of the saturated hydrocarbon solvent having 8 to 15 carbon atoms and the aromatic hydrocarbon solvent having 8 to 15 carbon atoms is preferably 100/0 to 50/50, more preferably from the viewpoint of odor and volatility. 100/0 to 80/20, more preferably 100/0. Component (a-3) dissolves and disperses components (a-1) and (a-2) described above, and is substantially present in layer (I) by evaporation after coating. It is something that does not. By setting the carbon number of the saturated hydrocarbon solvent to 8 to 15, the components (a-1) and (a-2) can be dissolved and dispersed well. In addition, the balance between the volatility and the viscosity, which greatly affects the workability during application, can be improved. If the number of carbon atoms is less than the above lower limit, the volatility is too high, and the coating operation must be performed extremely quickly, resulting in poor workability. On the other hand, if the number of carbons exceeds the above upper limit, the volatility decreases, and not only does it take a long time to move to the subsequent step, for example, the application of the finishing agent (B), but also the obtained film forming agent. The viscosity of (A) becomes high, and it becomes difficult to form a smooth coating film when the agent is applied manually. Examples of the solvent include n-octane, iso-octane, n-nonane, iso-nonane, n-decane, iso-decane, n-undecane, iso-undecane, n-dodecane, iso-dodecane, and n-tridecane. , Iso-tridecane, n-tetradecane, iso-tetradecane, n-pentadecane, iso-pentadecane, and a structural compound of normal paraffin or isoparaffin having a linear or branched chain. Of these, an isoparaffin-based solvent is preferably used. These solvents may be used alone or in combination. In order to adjust the flash point, volatility, etc., it can be selected as appropriate. On the other hand, the aromatic hydrocarbon solvent having 8 to 15 carbon atoms is an organic solvent composed of a compound having an aromatic ring other than the saturated hydrocarbon solvent, and the carbon number of the main component in the distillate fraction of crude oil. Is in the range of 8-15. For example, mesitylene, hemimeritene, pseudocumene, ethyltoluene, cumene, preniten, isodurene, durene, propylbenzene, meritene, cymene, bibenzyl and the like can be mentioned. As the aromatic hydrocarbon solvent, commercially available products can be used, and preferably, Ipsol 100 (mainly composed of aromatic hydrocarbons having 9 carbon atoms), Ipsol 150 (carbon number) produced by Idemitsu Kosan Co., Ltd. 10 based on aromatic hydrocarbons (both are trademarks), SWAZOL 1000 manufactured by Maruzen Petrochemical Co., Ltd. (based on aromatic hydrocarbons having 8 to 10 carbon atoms) (trademark), ExxonMobil Chemical Solvesso 100 (dialkyl and trialkylbenzene having 9 to 10 carbon atoms), Solvesso 150 (mainly alkylbenzene having 10 to 11 carbon atoms), Solvesso 200 (mainly alkylnaphthalene having 10 to 14 carbon atoms) ) (Both are trademarks), Cactus Solvent P-100 manufactured by Japan Energy Co., Ltd. Zen), Cactus solvent P-180 (mixture of methylnaphthalene and dimethylnaphthalene), Cactus solvent P-200 (mixture of methylnaphthalene and dimethylnaphthalene), Cactus solvent P-220 (mixture of methylnaphthalene and dimethylnaphthalene) (all (Trademark), Shellsol A150 (mixture of naphthalene and trimethylbenzene) (trademark) manufactured by Shell Chemical Co., etc. are particularly preferred.

(A-1) a polyorganosiloxane having one or more hydrolyzable functional groups in the molecule, (a-2) a curing catalyst, and (a-3) a saturated hydrocarbon solvent having 8 to 15 carbon atoms, The blending amount of the organic solvent consisting of the aromatic hydrocarbon solvent having 8 to 15 carbon atoms as an optional component is as follows. The compounding amount of the component (a-1) is 45 parts by mass, preferably 30 parts by mass with respect to 100 parts by mass in total of the components (a-1), (a-2) and (a-3). The lower limit is 3 parts by mass, preferably 5 parts by mass, more preferably 7 parts by mass. If it is less than the lower limit, a tough cured film cannot be formed. If the upper limit is exceeded, workability at the time of application decreases, and in addition, it becomes difficult to form a smooth film.

The compounding amount of the component (a-2) is 5 parts by mass, preferably 3 parts by mass with respect to a total of 100 parts by mass of the components (a-1), (a-2), and (a-3). The lower limit is 0.05 parts by mass, preferably 0.5 parts by mass. If it is less than the said minimum, hardening will become inadequate and a favorable film will not be formed, on the other hand, if it exceeds the said upper limit, the storage stability of a film formation agent (A) will worsen.

The compounding quantity of a component (a-3) is adjusted so that the sum total of a component (a-1), (a-2) and (a-3) may be 100 mass parts. That is, the upper limit of the blending amount of the component (a-3) is 96.95 parts by mass, preferably 100 parts by mass in total of the components (a-1), (a-2), and (a-3). Is 95 parts by mass, and the lower limit is 50 parts by mass. If it is less than the said minimum, since the viscosity of a film formation agent (A) will become high too much, it will become difficult to form a smooth film.

In the present invention, the layer (I) obtained by curing the film forming agent (A) containing the components (a-1), (a-2), and (a-3) is provided on the substrate side. The film-forming agent (A) can form the layer (I) by being applied to a substrate directly or via another layer and cured. The film forming agent (A) is preferably applied directly onto the substrate. In the layer (I), the component (a-1) exhibits strong adhesion due to a chemical reaction with the member to be coated. In addition, the component (a-1) itself causes a crosslinking reaction and is cured, thereby imparting particularly excellent water repellency to the entire coating layer.

The (b-1) polyorganosiloxane contained in the finishing agent (B) may be one having at least one amino group in the molecular side chain. In addition, (b-1) may have an amino group at the end of the molecular chain, but when (b-2) below has an amino group in the molecular side chain, (b-1) is a molecular chain. Does not have two or more amino groups. The component (b-1) is obtained by bringing the layer (II) obtained by applying the finishing agent (B) into close contact with the layer (I) obtained by applying the film forming agent (A). Water repellency is expressed in the entire coating layer. The upper limit of the functional group equivalent of the component (b-1) polyorganosiloxane is preferably 100,000, more preferably 10,000, and the lower limit is preferably 300, more preferably 500. The viscosity (25 ° C.) of the component (b-1), a value measured in accordance with JIS Z 8803, the upper limit is preferably 30,000 mm ² s ^-1, more preferably 3,000 mm ² s ^{- 1} and the lower limit is preferably 10 mm ² s ⁻¹ , more preferably 50 mm ² s ⁻¹ . If the above upper limit is exceeded, the viscosity of the entire finishing agent (B) may be high, and a smooth and uniform layer may not be applied. A smooth and uniform layer may not be applied. As the component (b-1), one of these may be used alone, or two or more may be used in combination.

The component (b-2) polyorganosiloxane of the present invention only needs to have two or more amino groups at the end of the molecular chain. The component (b-2) causes the entire coating layer to exhibit water repellency together with the component (b-1). The upper limit of the functional group equivalent of component (b-2) polyorganosiloxane is preferably 10,000, more preferably 5,000, and the lower limit is preferably 50, more preferably 100. Moreover, the viscosity (25 degreeC) of a component (b-2) is the value measured based on JISZ8803, Preferably an upper limit is 1,000 mm < ² > s ^<-1> , More preferably, it is 500 mm < ² > s ^<-1> . Yes, the lower limit is preferably 1 mm ² s ⁻¹ , more preferably 10 mm ² s ⁻¹ . If the above upper limit is exceeded, the viscosity of the entire finishing agent (B) may be high, and a smooth and uniform layer may not be applied. A smooth and uniform layer may not be applied. As the component (b-2), one of these may be used alone, or two or more may be used in combination.

The (b-3) silicone resin emulsion emulsified with a nonionic or anionic surfactant of the present invention is obtained by emulsifying a silicone resin having a polyorganosiloxane skeleton with a nonionic or anionic surfactant, In order to smoothen the layer (II) obtained by curing the finishing agent (B), the finishing agent (B) is provided with slipperiness. The component (b-3) preferably contains a solid content of 5 to 90% by mass, more preferably 10 to 50% by mass. Here, (b-3) The upper limit of the pH of the silicone resin emulsion is preferably 6.4, more preferably 6.1, and the lower limit is preferably 4.0, more preferably 5.0. If the pH exceeds the upper limit, the emulsion becomes unstable, and if the pH is lower than the lower limit, the surface of the coated member may be affected. As the component (b-3), for example, trimethylsiloxysilicic acid having a viscosity of 2,000 cSt (25 ° C.) is dissolved in dimethylpolysiloxane having a viscosity of 350 cSt, and further emulsified and dispersed in water with a nonionic surfactant. [Trimethylsiloxysilicic acid content: 12% by mass, dimethylpolysiloxane content: 28% by mass, pH: 6, R2701 (trademark) manufactured by Asahi Kasei Wacker Silicone Co., Ltd.], emulsion of silicone resin oil [solid content: 40 mass%, pH: 6, NP2804 (trademark) manufactured by Asahi Kasei Wacker Silicone Co., Ltd., aminosilicone emulsion [solid content: 40 mass%, pH: 6, NP2609 (trademark) manufactured by Asahi Kasei Wacker Silicone Co., Ltd.] and the like. .

(B-4) The hydrophilic group-containing organic solvent dissolves and disperses the above components (b-1), (b-2), and (b-3). II) is substantially absent. The hydrophilic group is a functional group that contributes to hydration such as OH group, COOH group, NH ₂ group, etc., and the hydrophilic group-containing organic solvent is an organic solvent composed of a compound that is compatible with water at an arbitrary ratio. That is. Examples of the component (b-4) include methanol, ethanol, n-propanol, iso-propanol, butanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, methyl cellosolve, ethyl cellosolve, 1,3-butanediol. 1,4-butanediol, hexanetriol, glycerin, neopentyl glycol, pentaerythritol and other alcohols that are compatible with water are particularly preferably used. These solvents may be used alone or in combination. Moreover, it can select suitably from these and can adjust a viscosity, flash point, volatility, etc.

(B-5) Water is volatilized by dissolving or dispersing the above components (b-1), (b-2), (b-3) and (b-4) constituting the finishing agent (B). Used to improve the balance between stability and storage stability, and evaporates after application and is substantially absent in layer (II).

(B-1) polyorganosiloxane having one or more amino groups in the molecular side chain, (b-2) polyorganosiloxane having two or more amino groups at the molecular chain end, (b-3) nonionic or anion The blending amounts of the silicone resin emulsion emulsified with the system surfactant, (b-4) the hydrophilic group-containing organic solvent, and (b-5) water are as follows. The compounding amount of component (b-1) is 100 parts by mass in total of components (b-1), (b-2), (b-3), (b-4), and (b-5). The upper limit is 15 parts by mass, preferably 5 parts by mass, and the lower limit is 0.05 parts by mass, preferably 0.1 parts by mass. If it is less than the above lower limit, desired water repellency cannot be exhibited. On the other hand, if it exceeds the above upper limit, the storage stability is lowered.

The amount of component (b-2) is based on a total of 100 parts by mass of components (b-1), (b-2), (b-3), (b-4), and (b-5). The upper limit is 10 parts by mass, preferably 3 parts by mass, and the lower limit is 0.01 parts by mass, preferably 0.1 parts by mass. If it is less than the lower limit, good gloss cannot be exhibited. On the other hand, if the above upper limit is exceeded, the storage stability may be lowered. In the present invention, the upper limit of the total amount of components (b-1) and (b-2) is preferably 20 parts by weight. By controlling the total amount of components (b-1) and (b-2) in this way, water repellency and gloss can be exhibited while having good storage stability.

The compounding amount of component (b-3) is 100 parts by mass in total of components (b-1), (b-2), (b-3), (b-4), and (b-5). The upper limit is 20 parts by mass, preferably 15 parts by mass, and the lower limit is 1 part by mass, preferably 3 parts by mass. If the amount is less than the above lower limit, the desired slip property cannot be exhibited. On the other hand, if the amount exceeds the above upper limit, the finishing agent (B) aggregates and storage stability is lowered.

The compounding amount of component (b-4) is 100 parts by mass in total of components (b-1), (b-2), (b-3), (b-4), and (b-5). The upper limit is 25 parts by mass, preferably 15 parts by mass, and the lower limit is 0.1 parts by mass, preferably 1 part by mass. If it is less than the above lower limit, the components (b-1) and (b-2) cannot be sufficiently dissolved and dispersed, and the workability is reduced because the overall volatility of the finishing agent (B) is reduced. Deteriorate. On the other hand, when the above upper limit is exceeded, the emulsion of component (b-3) becomes unstable and not only the storage stability of the finishing agent (B) is lowered, but also the volatility is increased. The time required to complete the coating operation of B) becomes too short and the workability deteriorates.

The amount of component (b-5) is such that the sum of components (b-1), (b-2), (b-3), (b-4), and (b-5) is 100 parts by mass. Adjusted to be. That is, the total amount of components (b-5), (b-2), (b-3), (b-4), and (b-5) is 100 masses. The upper limit is 98.84 parts by mass with respect to parts, and the lower limit is 30 parts by mass, preferably 70 parts by mass. By making it into this range, the balance between the volatility and the storage stability of the finishing agent (B) can be improved.

Moreover, various components can be mix | blended with the finishing agent (B) of this invention as needed in the range which does not impair the effect of this invention. Examples thereof include rust preventives, preservatives, surfactants, pH adjusters, antifreeze agents, ultraviolet absorbers, and stabilizers.

In the present invention, the finishing agent (B) containing the components (b-1), (b-2), (b-3), (b-4), and (b-5) is added to the layer (I The layer (II) can be formed by coating on and solidifying. The layer (II) thus obtained can increase the volatility and gloss by interacting with the layer (I). In addition, since the layer (II) can be a thick film, the inhomogeneous portion of the layer (I) can be filled into a smooth coating layer as a whole.

The film forming agent (A) and the finishing agent (B) are applied onto the substrate as described below, and are cured and solidified, respectively. The film-forming agent (A) is preferably applied using a dry cloth onto the substrate or other layers already applied on the substrate. Here, the dry cloth is usually a cloth having a moisture content of 20% or less, more preferably a moisture content of 5% or less, for example, a fabric made of synthetic fibers such as polyester, nylon, polyester / nylon composite fiber, polyurethane, polyvinyl chloride, and cotton. , Fabrics made of natural fibers such as silk, hemp, rayon, cashmere and mohair. In view of the balance between the strength of the fiber and the permeability of the coating liquid, a fabric made of synthetic fibers selected from polyester, nylon, and polyester / nylon composite fibers is particularly preferable. Although the usage-amount of a film formation agent (A) changes with kinds of base material etc. and the kind of agent to apply | coat, it is 0.1-10 milliliters per 1 m < ² > of application areas normally. Application to a substrate or the like is usually carried out using a dry cloth by human power, but of course, it can also be carried out mechanically. The film-forming agent (A) applied in this way forms a cured film as the crosslinking reaction proceeds at ambient temperature for 5 to 90 minutes, preferably 10 to 30 minutes. In this way, the layer (I) obtained by curing the film forming agent (A) is formed. The thickness of the layer (I) can be appropriately changed depending on the amount of the film forming agent (A) used, but is usually 0.1 to 0.5 μm.

Next, a finishing agent (B) is applied onto the layer (I). The application of the finishing agent (B) is preferably carried out using a poultice. Here, as the compress, the water retention rate specified in JIS L 1906 is 600% or less, more preferably in the range of 190 to 230%, and the water absorption rate specified in JIS L 1907 is 4 seconds or less, preferably 2 Particularly preferred is a fabric containing 50% or more of water in a fabric of seconds or less. As the dry cloth, the cloth used as the poultice is made of synthetic fibers such as polyester, nylon, polyester / nylon composite fiber, polyurethane, polyvinyl chloride, cotton, silk, hemp, rayon, cashmere, mohair, etc. And a cloth made of natural fibers. These fabrics preferably have water absorption and water retention within the above specified ranges. The amount of the finishing agent (B) used can be changed in consideration of the smoothness of the layer (I) obtained by curing the film forming agent (A), but is usually 0 per 1 m ^{2 of} the coating area. .1 to 10 milliliters. As described above, the application is usually carried out using a poultice by human power, but of course, it can also be carried out mechanically. The finish treatment agent (B) is dried and solidified at an ambient temperature for 10 minutes or more, preferably 30 minutes or more and 240 minutes or less after application to form a film. In this way, the layer (II) obtained by solidifying the finishing agent (B) is formed. Although the thickness of layer (II) can be suitably changed with the usage-amount of a finishing processing agent (B), it is 0.1-0.5 micrometer normally.

In the present invention, there are no particular limitations on the type of substrate on which the coating layer is formed. For example, it is formed on the exterior of a vehicle, preferably on the painted surface of an automobile. The amount of the film-forming agent (A) and the finishing agent (B) used when applied to the painted surface of an automobile is a general guideline, for example, about 50 milliliters for light vehicles, and 60 to 70 milliliters for ordinary vehicles. It is about 80 ml for a minivan. Further, in the present invention, a new layer may be provided by applying a film forming agent made of a composition having other film forming ability between the layer (I) and the layer (II). It is allowed that the agent is the film forming agent (A) of the present invention, that is, the film forming agent is repeatedly applied. Further, the present invention allows a new layer to be provided on the surface after the layer (II) is applied.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples.

[Preparation of film forming agent (A) and finishing agent (B)]
Substances The substances used for the preparation of the film forming agent (A) and the finishing agent (B) are as follows.

<Component (a-1): Polyorganosiloxane having one or more hydrolyzable reactive groups in the molecule>
(I) Methoxy-functional polydimethylsiloxane [X-40-9225 (trademark) manufactured by Shin-Etsu Chemical Co., Ltd., polydimethylsiloxane having methoxy groups at both molecular side chains and molecular chain ends, methoxy group content: 24% by weight Viscosity (value measured according to JIS Z 8803): 100 mm ² s ⁻¹ ]
(Ii) Methoxy-functional polydimethylsiloxane [X-40-9250 (trademark) manufactured by Shin-Etsu Chemical Co., Ltd., polydimethylsiloxane having methoxy groups at both molecular side chains and molecular chain ends, methoxy group content: 25% by weight , Viscosity (value measured according to JIS Z 8803): 160 mm ² s ⁻¹ ]
(Iii) Methoxy functional methyl / phenyl substituted polysiloxane [KR-401N (trademark) manufactured by Shin-Etsu Chemical Co., Ltd., methyl / phenyl substituted polysiloxane having methoxy groups at both molecular side chains and molecular chain ends, methoxy group content : 33 wt%, viscosity (value measured according to JIS Z 8803): 20 mm ² s ⁻¹ ]
(Iv) Methoxy functional methyl / phenyl substituted polysiloxane [KR-510 (trademark) manufactured by Shin-Etsu Chemical Co., Ltd., methyl / phenyl substituted polysiloxane having methoxy groups at both molecular side chains and molecular chain ends, methoxy group content : 17% by weight, viscosity (value measured in accordance with JIS Z 8803): 100 mm ² s ⁻¹ ]

<Comparison component (a-1)>
(I) Both ends methyl group-blocked polydimethylsiloxane [KF-96-100CS (trademark) manufactured by Shin-Etsu Chemical Co., Ltd., viscosity (value measured according to JIS Z 8803): 100 mm ² s ⁻¹ ]

<Component (a-2): Curing catalyst containing organometallic compound>
(I) Titanium alkoxide [D-20 (trademark) manufactured by Shin-Etsu Chemical Co., Ltd., metal content: 21% by weight]
(Ii) Titanium alkoxide [D-25 (trademark) manufactured by Shin-Etsu Chemical Co., Ltd., metal content: 14% by weight]
(Iii) Aluminum alkoxide [DX-9740 (trademark) manufactured by Shin-Etsu Chemical Co., Ltd., metal content: 9% by weight]

<Component (a-3): C8-15 saturated hydrocarbon solvent>
(I) Isoparaffinic hydrocarbon solvent [Isoper M (trademark) manufactured by ExxonMobil, distillation temperature range: 225 to 254 ° C., flash point: 92 ° C. mainly containing isoparaffin hydrocarbons having 12 to 15 carbon atoms]
(Ii) Isoparaffinic hydrocarbon solvent [Isoper L (trademark) manufactured by ExxonMobil Co., Ltd., mainly composed of isoparaffinic hydrocarbon having 11 to 13 carbon atoms, distillation temperature range: 185 to 199 ° C., flash point: 64 ° C.]
(Iii) Aromatic hydrocarbon solvents [Solvesso 150 (trademark) manufactured by ExxonMobil, heavy aromatic solvent naphtha comprising a mixture of aromatic hydrocarbons having 8 to 12 carbon atoms, distillation temperature range: 189 to 210 ° C., Flash point: 65 ° C]

<Comparative component (a-3)>
(I) Isoparaffinic hydrocarbon solvent [IP Clean HX (trademark) manufactured by Idemitsu Kosan Co., Ltd., distillation temperature range: 211 to 255 ° C., flash point: 84 ° C. based on isoparaffinic hydrocarbon having 16 carbon atoms]
(Ii) Isohexene [isoolefin hydrocarbon having 6 carbon atoms, boiling point: 62 ° C., flash point: −26 ° C.] (isohexene manufactured by Wako Pure Chemical Industries, Ltd.)
(Iii) Isopropyl alcohol [ExxonMobil IPA (trademark) manufactured by ExxonMobil, distillation temperature: 80 ° C., flash point: 0 ° C. or less]
(Iv) Ethylene glycol dimethyl ether [distillation temperature: 82 to 83 ° C., flash point: −1.5 ° C.] (ethylene glycol dimethyl ether manufactured by Nacalai Tesque Co., Ltd.)

<Component (b-1): Polyorganosiloxane having one or more amino groups in the silicone side chain>
(I) Side chain type monoamine-modified polysiloxane [KF-865 (trademark) manufactured by Shin-Etsu Chemical Co., Ltd., functional group equivalent: 5,000 gmol ⁻¹ , viscosity (value measured according to JIS Z 8803): 110 mm ² s ⁻¹ , has no amino group at the end of the molecular chain]
(Ii) Side chain type diamine-modified polysiloxane [KF-880 (trademark) manufactured by Shin-Etsu Chemical Co., Ltd., functional group equivalent: 1,800 gmol ⁻¹ , viscosity (value measured according to JIS Z 8803): 650 mm ² s ⁻¹ , has no amino group at the end of the molecular chain]
(Iii) Side chain type amino polyether modified polysiloxane [Shin-Etsu Chemical Co., Ltd. X-22-3939A (trademark), functional group equivalent: 1,500 gmol ⁻¹ , viscosity (measured according to JIS Z 8803] Value): 3,300 mm ² s ⁻¹ , having no amino group at the end of the molecular chain]

<Comparative component (b-1)>
(I) Side chain type epoxy-modified polysiloxane [X-22-343 (trademark) manufactured by Shin-Etsu Chemical Co., Ltd., functional group equivalent: 525 gmol ⁻¹ , viscosity (value measured according to JIS Z 8803): 25 mm ² s ⁻¹ ]
(Ii) Side chain type epoxy ether both-modified polysiloxane [Shin-Etsu Chemical Co., Ltd. X-22-4741 (trademark), functional group equivalent: 2500 gmol ⁻¹ , viscosity (value measured according to JIS Z 8803 ): 350 mm ² s ⁻¹ ]

<Component (b-2): Polyorganosiloxane having two or more amino groups at the molecular chain terminal>
(I) Terminal diamino-modified polysiloxane [X-22-161B (trademark) manufactured by Shin-Etsu Chemical Co., Ltd., each having one amino group at both ends of the molecular chain, functional group equivalent: 1,500 gmol ⁻¹ , viscosity ( Value measured according to JIS Z 8803): 55 mm ² s ⁻¹ , having no amino group in the molecular side chain]

<Comparison component (b-2)>
(I) Terminal-type carboxyl-modified polysiloxane [X-22-162C (trademark) manufactured by Shin-Etsu Chemical Co., Ltd., functional group equivalent: 2,300 gmol ⁻¹ , viscosity (value measured according to JIS Z 8803): 220 mm ² s ^-1 ]
(Ii) Terminal silanol-modified polysiloxane [KF-9701 (trademark) manufactured by Shin-Etsu Chemical Co., Ltd., functional group equivalent: 1,500 gmol ⁻¹ , viscosity (value measured according to JIS Z 8803): 60 mm ² s ^-1 ]

<Component (b-3): Silicone resin emulsion emulsified with a nonionic or anionic surfactant>
(I) Anion-dispersible silicone resin emulsion [R2701 (trademark) manufactured by Asahi Kasei Wacker Silicone Co., Ltd., solid content 40%, pH 6]
(Ii) Nonionic dispersible silicone resin emulsion [NR2706 (trademark) manufactured by Asahi Kasei Wacker Silicone Co., Ltd., solid content 55%, pH 6]
(Iii) Nonionic dispersible amino-modified silicone resin emulsion [NP2609 (trademark) manufactured by Asahi Kasei Wacker Silicone Co., Ltd., solid content 40%, pH 6]

<Comparison component (b-3)>
(I) Cation dispersible silicone resin emulsion [Polon MF-52 (trademark) manufactured by Shin-Etsu Chemical Co., Ltd., solid content: 32%, pH 6.5]

<Component (b-4): Hydrophilic group-containing organic solvent>
(I) Isopropyl alcohol (ExxonMobil IPA manufactured by ExxonMobil)
(Ii) Normal propyl alcohol (normal propyl alcohol manufactured by Sankyo Chemical Co., Ltd.)
(Iii) Ethanol (ethanol produced by Sankyo Chemical Co., Ltd.)
(Iv) Ethylene glycol (ethylene glycol manufactured by Sankyo Chemical Co., Ltd.)

<Comparison component (b-4)>
(I) Ethylene glycol dimethyl ether (dimethyl emulsifier manufactured by Nippon Emulsifier Co., Ltd.)

<Preparation of film forming agent (A)>
Ingredients (a-1), (a-2) and (a-3), and comparative components (a-1) and (a-3) were used in the mixing ratios shown in Tables 1 and 2, respectively. The film forming agents (A-1) to (A-10) and the comparative film forming agents (A′-1) to (A′-9) were prepared by stirring and mixing at room temperature. Each film forming agent and comparative film forming agent were evaluated for storage stability and odor.

<Preparation of finishing agent (B)>
Components (b-1), (b-2), (b-3) and (b-4), and comparison components (b-1), (b-2), (b-3) and (b- 4) were mixed by stirring at room temperature using the blending ratios shown in Tables 3 and 4, respectively, to finish the finishing agents (B-1) to (B-11) and the comparative finishing agent (B′-1). ) To (B′-10) were prepared. Each finish and comparative finish was evaluated for dispersibility and storage stability.

The test methods used for evaluating each film-forming agent and comparative film-forming agent, and each finishing agent and comparative finishing agent are as follows.

<Storage stability>
The film forming agent (A) was filtered through a 200 mesh stainless steel sieve, and 100 ml was collected. The total amount of the collected film forming agent (A) was sealed in a glass container. Also, the finishing treatment agent (B) was filtered in the same manner as above, and 100 ml was collected. The whole amount of the collected finishing agent (B) was sealed in a polyethylene sealed container. Both the film-forming agent (A) and the finishing agent (B) were stored at 40 ° C. for 30 days, and then stored at −5 ° C. for 30 days. Subsequently, these external appearances were visually inspected and evaluated. The evaluation results of the film forming agent (A) and the finishing treatment agent (B) are indicated by the following symbols, respectively.
Evaluation results of the film forming agent (A):
○: No turbidity, discoloration, precipitation, or precipitation of crystalline substance was observed Δ: Any one of turbidity, discoloration, precipitation, or precipitation of crystalline substance was observed x: Turbidity of liquid Evaluation of the finishing agent (B): any one of two or more of the following:
○: Discoloration, dispersion aggregation, and separation of liquid phase were not observed Δ: Discoloration, dispersion aggregation, and separation of liquid phase were observed ×: Discoloration, dispersion of dispersion Any two or more of agglomeration and liquid phase separation were observed

<Odor>
The film forming agent (A) was collected in an approximately 20 ml glass container and sealed. This was allowed to stand at room temperature for 5 minutes, and then the odor was evaluated by opening and sniffing. The evaluation results are indicated by the following symbols.
○: Slightly felt odor Δ: Slightly felt odor ×: Slightly felt odor

<Dispersibility>
The finishing agent (B) was filtered through a 200 mesh stainless steel sieve, and 100 ml was collected. The finishing agent (B) thus collected was sealed in a polyethylene sealed container. These were left at room temperature and evaluated by visually observing a change in appearance over time. The evaluation results are indicated by the following symbols.
○: The liquid was kept in a uniform state even after 30 days. Δ: Aggregation and sedimentation were observed in 10 days or more and less than 30 days. X: Aggregation and sedimentation were observed in less than 10 days.

The above evaluation results are shown in Tables 1 and 2 and Tables 3 and 4, respectively.

Table 1 relates to the film-forming agent (A) of the present invention, and formulation examples (A-1) to (A-1) to (a-1), (a-2) and (a-3) in which the types and blending ratios are changed. (A-10) was shown. All showed good storage stability and odor. Of these, Formulation Example (A-10) is a component (a-3) comprising a solvent in which a saturated hydrocarbon solvent having a carbon number within the range of the present invention and an aromatic hydrocarbon solvent are blended at a predetermined ratio. It is what was used. Although the odor was somewhat felt, the effect of the present invention was not impaired.

On the other hand, Table 2 shows a blending example (A′-2) in which the blending ratio of the components (a-1), (a-2) and (a-3) is outside the scope of the present invention, and a comparison. The comparative film formation agent of (A'-1) and (A'-3)-(A'-9) which used component (a-1) and (a-3) was shown. In (A'-1), (A'-3), (A'-4) and (A'-9), relatively good results were obtained in both storage stability and odor. However, other comparative film forming agents resulted in poor storage stability or odor.

Table 3 shows the types and blends of the components (b-1), (b-2), (b-3), (b-4) and (b-5) regarding the finishing agent (B) of the present invention. Formulation examples (B-1) to (B-11) in which the ratio was changed were shown. All showed good dispersibility and storage stability. Among these, about the compounding example (B-10), although some discoloration etc. were seen, the effect of this invention was not impaired.

On the other hand, in Table 4, the compounding ratio of components (b-1), (b-2), (b-3), (b-4) and (b-5) is outside the scope of the present invention. Formulation examples (B′-1), (B′-2), (B′-9) and (B′-10), and comparison components (b-1), (b-2), (b-3) ) And (b-4) were used as comparative finishing treatment agents (B′-3) to (B′-8). In (B′-1) to (B′-6), good results were obtained in both dispersibility and storage stability. However, other than that, one or more of dispersibility and storage stability was a bad result.

(Examples 1-20 and Comparative Examples 1-16)
Film-forming agents (A-1) to (A-10) and comparative film-forming agents (A′-1) to (A′-9) prepared as described above, and finishing agent (B-1) ~ (B-11) and comparative finishing agents (B'-1) to (B'-10) are combined and carried out as shown in Tables 5 to 8 to facilitate wiping, water repellency (initial water repellency) , Durable water repellency and water repellency after storage) and gloss. The test methods used for evaluation of ease of wiping, water repellency and gloss are as follows.

<Ease of wiping>
On the painted surface of a black painted plate (material: SPCC-SD, standard: JIS-G-3141, dimensions: 0.8 mm x 70 mm x 150 mm, one-side acrylic coated after electrodeposition, manufactured by Asahi Bee Techno Co., Ltd.) The film-forming agents (A-1) to (A-10) shown in 5 to 8 and the comparative film-forming agents (A′-1) to (A′-9) were added in 3 drops (about 3 cc) using a dropper. ) Added dropwise. Next, a dry and clean cloth (a cloth made of a polyester / nylon composite fiber having a yarn diameter of 1 to 5 μm, moisture: 5% or less) is used to wipe the film-forming agent into a uniform thin film. Was applied. The black painted plate thus obtained was allowed to stand for 20 minutes in an environment of 23 ° C. and 65% RH to obtain a test piece (I) to which a film forming agent was applied.

Fine fiber cloths (fibers) in which the finishing agents (B-1) to (B-11) and comparative finishing agents (B′-1) to (B′-10) shown in Tables 5 to 8 are wetted with water. About 1 g was dropped in the vicinity of the center of a polyester / nylon composite fiber having a diameter of 300 dT or less. The fine fiber cloth was rubbed back and forth 10 times on the test piece (I) coated with the film-forming agent obtained as described above to obtain a test piece (II) treated with a finishing agent.

The evaluation of the ease of wiping was performed based on the sense of smoothness felt by the tester when the fine fiber cloth impregnated with the finishing agent was rubbed 10 times on the test piece (I) as described above. . For comparison, a black painted plate not coated with the film-forming agent (A) was also evaluated by rubbing 10 times on the black painted plate (Comparative Example 2). The evaluation results are indicated by the following symbols.
○: No catching feeling Δ: Some catching feeling ×: Very catching feeling

<Water repellency>
The water repellency was evaluated by the following initial water repellency, durable water repellency and water repellency after storage.

<Initial water repellency>
The test piece (II) produced as described above and treated with the finishing agent was left for 30 minutes in an environment of 23 ° C. and 65% RH. The contact angle of the treated surface of the test piece was determined by an automatic contact angle meter device (automatic contact angle meter DM500 (trademark) manufactured by Kyowa Interface Chemical Co., Ltd., droplet: 0.2 microliter, pure water, measurement: θ / 2 method. ) To measure and evaluate. The evaluation results are indicated by the following symbols.
A: Contact angle of 100 ° or more ○: Contact angle of less than 100 less than 95 ° Δ: Contact angle of less than 95 less than 85 ° x: Contact angle of less than 85 °

<Durable water repellency>
The test piece (II) produced as described above and treated with the finishing agent was left for 1 day in an environment of 23 ° C. and 65% RH. Next, the test piece was subjected to ASTM G154 accelerated weathering tester (ALTAS, Yubucon UC-1 type (trademark), using a fluorescent UV lamp, 1 cycle: UV irradiation (60 ° C. × 8 hours) + watering (50 ° C. × 4 Time)), treated for 1,000 hours, taken out, and evaluated by measuring the contact angle under the same conditions as the initial water repellency evaluation. The evaluation results are indicated by the following symbols.
A: Contact angle of 100 ° or more ○: Contact angle of less than 100 less than 95 ° Δ: Contact angle of less than 95 less than 85 ° x: Contact angle of less than 85 °

<Water repellency after storage>
The film forming agent (A) and the finishing agent (B) whose storage stability was evaluated as described above were used. The film forming agent (A) was applied by the same method as the evaluation of the ease of wiping, and then treated with a finishing agent (B) to obtain a test piece (III). The test piece (III) was evaluated by measuring the contact angle under the same conditions as in the evaluation of the initial water repellency. The evaluation results are indicated by the following symbols.
A: Contact angle of 100 ° or more ○: Contact angle of less than 100 less than 95 ° Δ: Contact angle of less than 95 less than 85 ° x: Contact angle of less than 85 °

<Glossy>
The test piece (II) produced as described above and treated with the finishing agent was left for 30 minutes in an environment of 23 ° C. and 65% RH. The gloss of the treated surface of the test piece was measured according to the specular gloss measurement method specified in JIS Z 8741. The specular glossiness measuring apparatus used for the measurement was Gloss Checker IG-331 (trademark) manufactured by Horiba. The evaluation results are indicated by the following symbols.
A: Specular gloss measurement value of 90 ° or more ◯: Specular gloss measurement value of 85 ° or more and less than 90 ° Δ: Specular gloss measurement value of 80 ° or more and less than 85 ° x: Specular glossiness The measured value is less than 80 °

The above evaluation results are shown in Tables 5-8. In the evaluation results, those having 3 or more Δ and those having 1 or more × were determined to be defective. In the following table, Comparative Example 1 is not subjected to treatment with a finishing agent. In Comparative Example 1, the film-forming agent was applied to form a uniform thin film as described above, and after 10 minutes, the surface was lightly rubbed with a clean dry fine fiber cloth. After being left in a 65% RH environment for 1 day, the initial water repellency was evaluated by measuring the contact angle using the same automatic contact angle meter as described above. The durable water repellency was treated in the same manner as in the initial water repellency of Comparative Example 1 above, and further allowed to stand in an environment of 23 ° C. and 65% RH for 1 day, and then the same ASTM G154 accelerated weathering tester as described above. Then, the contact angle was measured and evaluated using the same automatic contact angle meter as described above. As for the water repellency after storage, the film forming agent (A) whose storage stability was evaluated was used, and the film forming agent was formed into a uniform thin film as in the case of the initial water repellency of Comparative Example 1 above. After 10 minutes from application, the surface is lightly rubbed with a dry clean fine fiber cloth, and then left for 1 day in an environment of 23 ° C. and 65% RH. Used to measure and evaluate the contact angle. For the gloss, using a test piece treated in the same manner as the initial water repellency, the test piece was allowed to stand in an environment of 23 ° C. and 65% RH for 30 minutes in the same manner as the gloss evaluation. It measured using the glossiness measuring apparatus. In Comparative Example 2, the treatment with the film forming agent (A) was not performed, and the black coating plate was directly subjected to the finishing treatment (B). In Comparative Example 15 (* 2 in Table 8), after applying the film forming agent (A-1) using a dry and clean cloth in the same manner as described in the item of ease of wiping above, In addition, a new dry cloth of the same kind is used to perform the treatment with the finishing agent (B-1). Further, Comparative Example 16 (* 1 in Table 8) is a film forming agent (A-1) using a fine fiber cloth wetted with water in the same manner as described in the item of the ease of wiping. After the coating, a fine fiber cloth wetted with the same kind of new water was used to perform the treatment with the finishing agent (B-1).

* 1: Using a fine fiber cloth wetted with water and coated with a film-forming agent (A-1) * 2: Using a dry cloth, treat with finishing agent (B-1) What

Examples 1 to 10 shown in Table 5 use the formulation examples (A-1) to (A-10) shown in Table 1 as the film forming agent (A), and the finishing agent (B). As an example, the blending example (B-1) shown in Table 3 is used. All showed good properties. On the other hand, the comparative example 1 did not use a finishing agent (B). It was found that a coating layer having good properties could not be obtained only with the film forming agent (A), and a coating layer having extremely good properties could be obtained when combined with the finishing agent (B) of the present invention. Examples 11 to 20 shown in Table 6 use the formulation example (A-1) shown in Table 1 as the film forming agent (A), and show in Table 3 as the finishing agent (B). Formulation examples (B-2) to (B-11) are used. In any case, the obtained coating layer exhibited good properties. On the other hand, in Comparative Example 2, the film forming agent (A) was not used. Even when only the finishing agent (B) was used, it was found that a coating layer having good properties could not be obtained unless it was used in combination with the film forming agent (A).

On the other hand, Comparative Examples 3 to 6 in Table 7 show that the finishing agent (B-1) of the present invention and the comparative film forming agents (A′-1), (A′-3), (A′-4) and ( A′-9). The comparative film-forming agents (A′-1), (A′-3), (A′-4) and (A′-9) were relatively good in both storage stability and odor. The properties of the resulting coating layer were not good. Comparative Examples 7 to 12 in Table 8 are combinations of the film forming agent (A-1) of the present invention and the comparative finishing agents (B'-1) to (B'-6). The comparative finishing agents (B′-1) to (B′-6) have obtained good results in both dispersibility and storage stability, but the properties of the obtained coating layers are not good. It was. In Comparative Example 13, a comparative film forming agent (A′-1) and a comparative finishing agent (B′-1) were used in combination. (A'-1) was good in both storage stability and odor, and (B'-1) was also good in dispersibility and storage stability, but the properties of the coating layer obtained from these were remarkably good. It was bad. Comparative Example 14 uses the film-forming agent (A-1) and the finishing agent (B-1) of the present invention, and after first coating (B-1) on the substrate, (A-1) is applied. The properties of the resulting coating layer were extremely poor. Comparative Examples 15 and 16 both use the film forming agent (A-1) and the finishing agent (B-1) of the present invention. In Comparative Example 15, a dry cloth was used and treated with the finishing agent (B-1). In Comparative Example 16, a fine fiber cloth wetted with water was used, and a film forming agent was used. (A-1) is applied. In any case, the properties of the obtained coating layer were poor.

The coating layer of the present invention can impart excellent water repellency and good gloss to a substrate such as a vehicle exterior. In addition, the coating layer forming method of the present invention is not only excellent in storage stability of the agent used and excellent in workability at the time of application, but the obtained coating layer can be applied to a substrate such as a vehicle exterior. Excellent water repellency and good gloss can be imparted. Therefore, it is expected that the coating layer and the method for forming the coating layer of the present invention will be greatly used in the future for coating of automobile exteriors and the like.

Claims (12)

(A-1) 3-45 parts by mass of a polyorganosiloxane having one or more hydrolyzable functional groups in the molecule,
(A-2) Curing catalyst 0.05-5 parts by mass, and
(A-3) A mass composed of a saturated hydrocarbon solvent having 8 to 15 carbon atoms and an aromatic hydrocarbon solvent having 8 to 15 carbon atoms, and the mass of the saturated hydrocarbon solvent and the aromatic hydrocarbon solvent. The film forming agent (A) containing a total of 100 parts by mass of 50 to 96.95 parts by mass of an organic solvent having a ratio of 100/0 to 50/50
Layer (I) obtained by curing
And
(B-1) 0.05 to 15 parts by mass of a polyorganosiloxane having one or more amino groups in the molecular side chain,
(B-2) 0.01 to 10 parts by mass of a polyorganosiloxane having two or more amino groups at the molecular chain terminal,
(B-3) Silicone resin emulsion emulsified with a nonionic or anionic surfactant 1 to 20 parts by mass as a solid content,
(B-4) Finishing agent (B) containing a total of 100 parts by mass of a hydrophilic group-containing organic solvent 0.1 to 25 parts by mass and (b-5) 30 to 98.84 parts by mass of water
Layer obtained by solidifying (II)
A coating layer comprising at least a layer (I) on the substrate side and a layer (II) on the surface side. The coating layer according to claim 1, comprising a layer (I) on the substrate and a layer (II) thereon. The coating layer according to claim 1 or 2, wherein the saturated hydrocarbon solvent having 8 to 15 carbon atoms constituting the component (a-3) is an isoparaffin solvent. The coating layer as described in any one of Claims 1-3 whose component (b-4) is alcohol. The coating layer according to any one of claims 1 to 4, wherein the component (a-1) is polydimethylsiloxane having hydrolyzable functional groups at both ends of the molecular chain. The coating layer according to any one of claims 1 to 5, wherein the substrate is a vehicle exterior. (A-1) 3-45 parts by mass of a polyorganosiloxane having one or more hydrolyzable functional groups in the molecule,
(A-2) Curing catalyst 0.05 to 5 parts by mass, and (a-3) consisting of a saturated hydrocarbon solvent having 8 to 15 carbon atoms and an aromatic hydrocarbon solvent having 8 to 15 carbon atoms, Film forming agent (A) comprising a total of 100 parts by mass of 50 to 96.95 parts by mass of an organic solvent in which the mass ratio of the saturated hydrocarbon solvent to the aromatic hydrocarbon solvent is 100/0 to 50/50
(I), which is applied onto a substrate and then dried at ambient temperature for 5 to 90 minutes to form layer (I),
And
(B-1) 0.05 to 15 parts by mass of a polyorganosiloxane having one or more amino groups in the molecular side chain,
(B-2) 0.01 to 10 parts by mass of a polyorganosiloxane having two or more amino groups at the molecular chain terminal,
(B-3) Silicone resin emulsion emulsified with a nonionic or anionic surfactant 1 to 20 parts by mass as a solid content,
(B-4) Finishing agent (B) containing a total of 100 parts by mass of a hydrophilic group-containing organic solvent 0.1 to 25 parts by mass and (b-5) 30 to 98.84 parts by mass of water
Step (II) in which layer (II) is applied on the layer (I) and then dried at ambient temperature for 10 minutes or more.
A coating layer forming method comprising at least: Application of the film forming agent (A) in the step (I) is performed using a dry cloth, and application of the finishing agent (B) in the step (II) is performed using a poultice. Item 8. The coating layer forming method according to Item 7. The coating layer forming method according to claim 7 or 8, wherein the saturated hydrocarbon solvent having 8 to 15 carbon atoms constituting component (a-3) is an isoparaffin solvent. The coating layer forming method according to any one of claims 7 to 9, wherein the component (b-4) is an alcohol. The coating layer forming method according to any one of claims 7 to 10, wherein the component (a-1) is polydimethylsiloxane having hydrolyzable functional groups at both ends of the molecular chain. The coating layer forming method according to any one of claims 7 to 11, wherein the substrate is a vehicle exterior.